WO2022191702A1 - Système pour produire de l'hydrogène ultrapur à partir d'ammoniac - Google Patents

Système pour produire de l'hydrogène ultrapur à partir d'ammoniac Download PDF

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Publication number
WO2022191702A1
WO2022191702A1 PCT/NL2022/050128 NL2022050128W WO2022191702A1 WO 2022191702 A1 WO2022191702 A1 WO 2022191702A1 NL 2022050128 W NL2022050128 W NL 2022050128W WO 2022191702 A1 WO2022191702 A1 WO 2022191702A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
ammonia
membrane reactor
heat
membranes
Prior art date
Application number
PCT/NL2022/050128
Other languages
English (en)
Inventor
Valentina CECHETTO
Luca DI FELICE
Fausto Gallucci
Original Assignee
Technische Universiteit Eindhoven
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technische Universiteit Eindhoven filed Critical Technische Universiteit Eindhoven
Priority to US18/280,911 priority Critical patent/US20240140789A1/en
Priority to EP22712086.2A priority patent/EP4304979A1/fr
Publication of WO2022191702A1 publication Critical patent/WO2022191702A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements

Definitions

  • the present invention relates to a system for producing hydrogen from ammonia.
  • the present invention also relates to the use of hydrogen thus produced.
  • Liquid fuels generated from hydrogen such as methanol, ammonia and formic acid could in fact be easily transported over long distances, stored next to H2 refueling stations for long time and H2 could be later recovered in-situ when required.
  • ammonia is a particularly promising hydrogen carrier due to its high volumetric energy density, relatively low cost and ease of liquefaction, storage and transportation compared to compressed hydrogen. Since it can be liquefied at higher temperature and lower pressure compared to hydrogen, ammonia liquefaction is in fact less energy intensive and, consequently, its storage and transportation can be carried out in smaller and lighter vessels compared to hydrogen. Moreover, the absence of carbon in its molecular structure makes ammonia an attracting and promising route for the production of H2 to be used in proton exchange membrane fuel cells (PEMFCs) for power production. In fact, while H2 traditionally produced from the reforming of fossil fuels in large scale plants inevitably contains CO x which are responsible for the poisoning of the cell electrodes (even when CO x concentrations are at ppms level) NH 3 is carbon-free.
  • PEMFCs proton exchange membrane fuel cells
  • CN 108854928 relates to a method for preparing a double-effect dense ceramic membrane reactor for hydrogen production by ammonia decomposition reaction and separation, which realizes that the decomposition reaction of ammonia and the purification of hydrogen are carried out simultaneously in the same unit.
  • Such method includes the following steps: preparation of tubular dense ceramic hydrogen permeable membrane, preparation of nickel catalyst with tubular dense ceramic hydrogen permeable membrane raw material as carrier, sleeve the quartz tube on the outside of permeable membrane, and the nickel catalyst is filled in the quartz tube and sealed with a sealing head to form a double-effect dense ceramic membrane reactor for ammonia decomposition hydrogen production reaction and separation.
  • An object of the present invention is to produce ultra-pure hydrogen that can be used to fuel cell applications or any other application which requires ultra- pure H2 as a feedstock.
  • An object of the present invention is to produce ultra-pure hydrogen in an energy friendly way wherein the production of heat and the consumption of heat is internally connected, i.e. a heat integrated construction.
  • An object of the present invention is to produce hydrogen in a continuous mode wherein the hydrogen thus produced has been stripped of unwanted impurities.
  • the present invention relates to a system for producing hydrogen from ammonia, the system comprising: a membrane reactor comprising membranes for selectively permeating hydrogen; adsorption columns for adsorbing ammonia; and a heat integration system configured to: supply heat to the inlet of the membrane reactor, recover heat from the outlet of the membrane reactor, and regenerate the absorption columns via the recovered heat.
  • the present inventors found that the hydrogen stored in its chemical bond has to be recovered through ammonia decomposition into H2 and N2. Subsequently, the H2 produced has to be separated from N2 and purified from possible traces of unconverted ammonia in order to meet the specifications required for a correct functioning of a specific application, such as a fuel cell.
  • the membrane reactor is an apparatus for reducing the footprint of conventional systems for efficient H2 recovery from NH 3.
  • NH 3 decomposition into H 2 and N 2 and high-purity H2 separation are simultaneously performed.
  • the selective H 2 separation performed by means of membranes shifts the thermodynamic equilibrium of reaction allowing the system to go beyond its thermodynamic constraint.
  • the membrane reactor comprises hydrogen selective membranes immersed in a catalyst bed.
  • the catalyst bed is a packed bed of particles or structured catalyst, especially a high thermal conductive structured or 3D structure including a metal having catalytic activity for ammonia decomposition.
  • the hydrogen selective membranes are positioned above the bottom of the catalyst bed located within the membrane reactor.
  • the hydrogen selective membranes are closed at its bottom side and open at its top side.
  • multiple adsorption columns are arranged for adsorption and regeneration functions.
  • the hydrogen selective membranes have a perm-selectivity H2/N2 of at least 5000, preferably >10.000.
  • system further comprises a burner for supplying the energy required for the decomposition of ammonia in hydrogen and nitrogen to the membrane reactor.
  • the residual heat of exhaust gases leaving the burner is used for heating up the ammonia feed to the membrane reactor.
  • the retentate from the membrane reactor is combusted in the burner.
  • the heat of the hydrogen permeated through the membranes is recovered and supplied to adsorption columns for regeneration thereof.
  • the output or effluent of adsorption columns in regeneration mode is combusted in the burner.
  • the hydrogen permeated through the membranes is supplied to adsorption columns for adsorbing impurities, such as unconverted ammonia.
  • the present invention also relates to hydrogen having a purity of at least 99,98 mol.% and an ammonia concentration of ⁇ 0.01 ppm as produced in a system as discussed above.
  • ultra-pure hydrogen refers to Ultrapure hydrogen according to ISO 14687:2019 and more specifically according to ISO 14687-2 and category 3 of ISO 14687-3.
  • the present invention also relates to a method for producing hydrogen from ammonia, comprising the following steps: supplying ammonia to a membrane reactor comprising membranes for selectively permeating hydrogen; decomposing ammonia in the membrane reactor into hydrogen and nitrogen; supplying hydrogen from the membrane reactor to adsorption columns for removing impurities from the hydrogen; wherein heat is supplied to the inlet of the membrane reactor and heat is recovered from the outlet of the membrane reactor, and regenerating the absorption columns via the recovered heat.
  • ammonia decomposition has been performed over a conventional Ru-based catalyst, while double-skin Pd-based membranes and zeolite 13X were used for hydrogen separation and hydrogen purification from residual NH3, respectively.
  • the preparation of the Pd-Ag membranes is carried out into two steps, wherein the first step consists in the coating of the porous supports and, specifically, it is carried out by co-depositing a Pd-Ag layer onto porous tubular alumina (a-A ⁇ Ch) asymmetric supports (14/7 mm OD/ID) with a top layer pore size of 100 nm from Rauschert Guy Veilsdor.
  • the co-deposition has been performed via electroless plating, a technique which consists of a first activation of the support with Pd seeds and a subsequent immersion of the support in a bath containing a Pd-Ag solution to produce the selective layer.
  • This layer proportionally increases with the plating time, therefore different plating times are set in order to obtain membranes with different permeation properties.
  • Two membranes have been used, one with selective layer of ⁇ 1 pm and one with selective layer of ⁇ 6-8 pm.
  • the second step of the membrane preparation consists in the deposition of a porous protective layer by dip-coating over the selective layer.
  • This protective layer which is a porous AI 2 O 3 -YSZ (yttria-stabilized zirconia) layer of 50 wt.% of YSZ with thickness of ⁇ 1 pm, aims at improving the membrane stability as it avoids any possible interaction between the selective layer and the catalyst in which the membrane will be immersed during application.
  • FIG.1 shows a process scheme of an embodiment of the system for producing hydrogen from ammonia according to the invention.
  • the same designations refer to equivalent parts;
  • FIG. 2 shows the influence of the introduction of a hydrogen cleaning unit on the purity of hydrogen produced from ammonia decomposition.
  • the ammonia feed (1) is heated up to the reaction temperature in a heat exchanger (2) where the residual heat of the exhaust gases leaving the burner (12) is exploited.
  • the cooled flue gases (18) leave then the system at temperature lower than 150 °C, whereas the heated feed (3) enters the membrane reactor (4) where hydrogen selective membranes (5) are immersed in a catalyst bed available in the form of small particles or 3D printed structures.
  • the membranes should preferably stay at least 10 cm above the bottom of the catalyst bed and are preferentially with a finger-like configuration (thus closed at the bottom).
  • the hydrogen permeated through the membranes (6) is first cooled down in a heat exchanger (7) and then (8) fed to an adsorption column (9) where ammonia is captured (adsorbed) and the ultra-pure hydrogen is produced (16).
  • the heat recovered from H2 cooling (15) is used to regenerate the sorbent in the column (10).
  • the comburent air is also used for the heat management of the system.
  • the pre heated air stream (15) is also used to regenerate the adsorption column (10) and the gas leaving column 10 (stream 18) is sent to the burner.
  • the cleaning system preferably consists of three columns. Column 9 is at low temperature and used to adsorb the traces of ammonia (and possibly other contaminants).
  • the outlet of this column is therefore pure hydrogen. While column 9 is used for hh purification and therefore is in “adsorption mode”, column 10 and column 19 are operated in the “regeneration mode”. A stream of hot air (15) is sent to column 10, in which thanks to the heat released by the air stream the previously adsorbed ammonia when the columns was used in hh purification mode is desorbed. The outlet (18) warm air containing traces of ammonia is then used as comburent in the burner. Column (19) is cooled with cold air (20) and the warm air available at its outlet is also sent to the burner. Preferably, the ratio between air stream 17 and air stream 20 is done such that each step of the three columns has the same time. In this way, it is therefore possible to switch the three columns between each other for continuous production of ultrapure hydrogen.
  • the hydrogen production unit includes two columns, which are simultaneously working, but into two different modes. While one column works for the removal of ammonia from the hydrogen stream, the other one works in regeneration mode.
  • the heat recovered from the cooling of both the permeate and retentate stream is exploited for the saturated sorbent regeneration, as high temperature favors ammonia desorption from the adsorbent material.
  • the off-gas leaving the regeneration column is sent to the burner to be combusted together with the retentate stream.
  • a column may also be fed with inert gas (nitrogen for instance) which could serve as a purge for ammonia that desorbs from the adsorbent material.
  • H2 separation tests for H2/NH3 mixtures have been carried out at lab scale in a membrane reactor where a Pd-based membrane with dead-end configuration was used for selective H2 separation. Goal of these experiment was to demonstrate that by forcing the produced H2 with traces of ammonia to pass through a column filled with adsorbent material it is possible to reduce the ammonia content of the stream and therefore produce ultra-pure H2 which can then be used as suitable fuel for systems requiring ultra-pure hydrogen. Different mixture compositions and permeation temperatures were selected. Specifically, H2 separation has been performed at 400°C, 425 °C and 450°C for H2/NH3 mixtures containing 5%, 10% and 15% of NH3.
  • the reactor was operated at 3 bar under a feed flow rate of 2 LN/min and the permeate side of the membrane was kept at atmospheric pressure.
  • the ammonia concentration at the permeate side of the membrane was connected to a purification stage, in which a bed of zeolite 13X was used as sorbent material for ammonia.
  • the ammonia concentration (ppm level) was measured upstream and downstream the hydrogen purification unit. The results of these tests show that by using a sorbent such as zeolite 13X for the removal of residual ammonia it is possible to reduce the NH3 concentration of the produced H2 stream to 0 ppm and consequently achieve the desired hydrogen purity.
  • the same result could also be obtained with any other adsorbent capable of adsorbing ammonia.
  • FIG. 2 Influence of the introduction of a hydrogen cleaning unit on the purity of hydrogen produced from ammonia decomposition. The experiment was carried out at 400 °C, 3 bar(a) and a feed flow rate of 2 LN/min of a H 2 /NH 3 mixture containing 95% (mol.) of hydrogen
  • the present invention thus relates to a system comprising a Pd based membrane reactor where the ammonia decomposition takes place and hydrogen (with low ppm of ammonia) is separated through the membrane.
  • the permeate side is treated in a Temperature Switch Adsorption (TSA) system comprising an adsorbent for the adsorption of the ammonia.
  • TSA Temperature Switch Adsorption
  • the heat in the permeate hydrogen and retentate is used to regenerate the ammonia sorbent by increasing the temperature.
  • the hydrogen exiting the system is ultrapure with (virtually) zero content in ammonia.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un système de production d'hydrogène à partir d'ammoniac, le système comprenant : un réacteur à membrane comprenant des membranes pour la perméation sélective de l'hydrogène ; des colonnes d'adsorption pour adsorber l'ammoniac ; et un système d'intégration de chaleur conçu pour : fournir de la chaleur à l'entrée du réacteur à membrane, récupérer la chaleur à la sortie du réacteur à membrane et régénérer les colonnes d'absorption par l'intermédiaire de la chaleur récupérée.
PCT/NL2022/050128 2021-03-09 2022-03-09 Système pour produire de l'hydrogène ultrapur à partir d'ammoniac WO2022191702A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US18/280,911 US20240140789A1 (en) 2021-03-09 2022-03-09 System to produce ultrapure hydrogen from ammonia
EP22712086.2A EP4304979A1 (fr) 2021-03-09 2022-03-09 Système pour produire de l'hydrogène ultrapur à partir d'ammoniac

Applications Claiming Priority (2)

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NL2027727 2021-03-09
NL2027727 2021-03-09

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002086987A2 (fr) * 2001-04-23 2002-10-31 Mesosystems Technology, Inc. Generateur d'hydrogene et son procede d'utilisation
CN108854928A (zh) 2018-07-05 2018-11-23 山东理工大学 氨分解制氢反应与分离双效致密陶瓷膜反应器的制备方法
CN111115572A (zh) * 2019-12-31 2020-05-08 浙江天采云集科技股份有限公司 一种mocvd制程含氨尾气制氢的非催化渗透性膜反应器及应用
CN111137853A (zh) * 2019-12-31 2020-05-12 四川天采科技有限责任公司 一种mocvd制程含氨尾气制氢的催化渗透性膜反应器、其制备方法及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002086987A2 (fr) * 2001-04-23 2002-10-31 Mesosystems Technology, Inc. Generateur d'hydrogene et son procede d'utilisation
CN108854928A (zh) 2018-07-05 2018-11-23 山东理工大学 氨分解制氢反应与分离双效致密陶瓷膜反应器的制备方法
CN111115572A (zh) * 2019-12-31 2020-05-08 浙江天采云集科技股份有限公司 一种mocvd制程含氨尾气制氢的非催化渗透性膜反应器及应用
CN111137853A (zh) * 2019-12-31 2020-05-12 四川天采科技有限责任公司 一种mocvd制程含氨尾气制氢的催化渗透性膜反应器、其制备方法及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LUBENAU U ET AL: "Wasserstoffqualitätsanforderungen", 20 November 2020 (2020-11-20), pages 1 - 32, XP055936124, Retrieved from the Internet <URL:https://www.dbi-gruppe.de/files/PDFs/Dokumente/11_GWB/2020_Bericht%20GWB_31.pdf> [retrieved on 20220628] *

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EP4304979A1 (fr) 2024-01-17

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